Detergent and cosmetic compositions comprising capryloyl glutamate salts and/oder capryloyl hydrolysate salts of wheat and/or rice protein

ABSTRACT

The invention describes detergent or cosmetic compositions provided with hydrating and preserving properties and simultaneously sebum regulating, anti-dandruff, and/or anti-odour properties. These compositions include a capryloyl glutamate salt and/or capryloyl hydrolysate of wheat and/or rice protein. Since the salt utilised is able also to provide a self-preservative and hydrating effect the compositions of the invention do not need any addition of further self-preservative or hydrating agents or, at most, contain concentrations thereof which are not efficacious per se.

The present invention relates to a detergent or cosmetic compositionprovided with sebum regulating, anti-dandruff and/or anti-odourproperties and simultaneously provided with hydrating andself-preservative properties.

In the formulation of cosmetic or detergent compositions with sebumregulating, anti-dandruff and/or anti-odour properties the use ofderivatives of caprylic acid is known. However, the problem with thederivatives commonly utilised is often that of excessively delipidisingthe corneal layer of the skin by acting as a solvent of the functionallipids contained in it and simultaneously removing the water-solublesubstances from it. All this causes excessive drying of the skin andfragility of the hair, which problems are commonly resolved by addingsuitable hydrating agents to the formulations. In the formulation ofcosmetic or detergent compositions in general it is moreover necessaryto add self-preservative agents which have the function of preservingthe composition from pollution by bacteria and other micro-organismssuch as, for example, fungi and yeasts, which can be the cause ofinfections in man. However, the disadvantage associated with the use ofself-preservative agents is that in order to be efficacious they mustoften be utilised at irritant concentrations or at concentrations atwhich they sensitise the tissue with which they come into contact.

The present invention therefore has the object of providing a detergentor cosmetic composition provided with the above indicated functionalproperties (that is to say, sebum regulating, anti-dandruff and/oranti-odour) which does not have the above-mentioned disadvantages.

This object has been achieved by the present inventors, who haveidentified various derivatives of caprylic acid which, when formulatedin detergent or cosmetic compositions, are not only able to perform thesebum regulating, anti-dandruff and/or anti-odour activity, but aresimultaneously able to confer on the said composition hydrating andself-preservative properties.

These derivatives are salts of capryloyl glutamate and capryloylhydrolysate of rice and/or wheat protein.

The salts of capryloyl glutamate can be obtained by the Schotten-Baumannreaction by making the amino group of the glutamic acid react withcapryloyl chloride in a basic environment, according to the followingreaction:

In the same way the salts of capryloyl hydrolysate can be obtained bymeans of the Schotten-Baumann reaction by making the amino group presentin the hydrolysate react with capryloyl chloride in a basic environmentaccording to the following reaction:

Wherein R is the peptide residue obtainable by means of hydrolysis ofwheat and/or rice proteins.

This peptide residue (or hydrolysate) is obtained by acid hydrolysis(with HCl) of gluten (wheat) and/or husks (rice) and subsequentfiltration to separate the product obtained from the drogs.

As an alternative to chemical hydrolysis, an enzymatic hydrolysis canalso be used, by exploiting the amylase and protease enzymes.

The product obtained from hydrolysis is a mixture of peptides having amolecular weight between 1000 and 4000 Dalton. In the ambit of thepresent specification this product will sometimes be indicated as“peptide residue” and other times as “hydrolysate of wheat and/or riceprotein”.

During the Schotten-Baumann reaction the dissociated carboxylic groupspresent are neutralised by salification with a base chosen in dependenceon the desired salt, for example NaOH or KOH. Alternatively, to obtainsalts of a weak base such as TEA the sodium or potassium salt is broughtto a pH of 2.0-3.0 with phosphoric acid to obtain the acid form andsubsequently dissolved in water and neutralised with the desired base.

In the above-described salts the dissociated carboxylic groups arepreferably neutralised with cations chosen from groups which consist of:cations belonging to the groups of alkaline metals or other monovalantcations such as Cu⁺; cations belonging to the groups of alkaline earthmetals or other bivalent cations such as Pb²⁺; trivalent cations such asAl³⁺; polyvalent cations such as Sn⁴⁺; NH₄ ⁺ or amine bases chosen fromtriethanol amine, monoethanol amine, diethanol amine, monoisopropanolamine, tri-isopropanol amine, 2-amino butanol, amino ethylpropanediol,arginine, lisine, ornithine, amino methyl propanol, amino methylpropanediol and 2-amino-2-hydroxymethyl-1,3-propanediol. Suchneutralising cations can also be utilised in combination with oneanother.

A subject of the invention is therefore the use of a salt of capryloylglutamate and/or capryloyl hydrolysate of wheat and/or rice proteins asself-preservative and hydrating agents and simultaneously sebumregulating, anti-dandruff and/or anti-odour agents in the formulation ofa detergent or cosmetic composition free from other self-preservativeagents and other hydrating agents, or including other self-preservativeand/or hydrating agents at a non-efficacious concentration and/orinsufficient to confer the desired characteristics of self-preservativeand/or hydration in an analogous or similar composition free of the saidcompounds (composition). Another subject of the invention is a detergentor cosmetic composition provided with hydrating and self-preservativeproperties and simultaneously sebum regulating, anti-dandruff and/oranti-odour properties, such sebum regulating, anti-dandruff and/oranti-odour agents including a composition which is a salt of capryloylglutamate and/or of capryloyl hydrolysate of wheat and/or rice protein,the said salt further having self-preservative and hydrating effect, thesaid composition therefore being free from other self-preservativeagents and other hydrating agents, or including other self-preservativeand/or hydrating agents at non-efficacious concentrations and/orinsufficient to confer the desired self-preservative and/or hydrationcharacteristics to an analogous or similar composition free from thesaid salt.

The expression “analogous or similar composition free from the saidsalt” is intended to indicate a composition constituted by the samecomponents in the same quantities as the composition of the invention,but which is differentiated from it by the fact that the capryloylglutamate salt and/or capryloyl hydrolysate salt of wheat and/or riceproteins is replaced by an equal quantity of other anionic surfactantagent.

In general it can be understood that a detergent or cosmetic compositionhas the desired self-preservative characteristic when it respondspositively to the tests for evaluation of the efficacy of the preservingpower. Such tests are conducted according to the indications provided bythe United States Pharmacopeia (USP) and/or by the Cosmetic, Toiletryand Fragrance Association (CTFA). These methods, and other similarmethods, involve the inoculation of the samples with micro-organisms ofdifferent types and counting the aerobic microbes of these at differenttimes to evaluate the survival level.

The self-preservative efficacy of the salts utilised in the presentinvention has been confirmed by means of challenge tests conducted onaqueous solutions of capryloyl glutamate in the form of sodium salt,inoculated with mixed inoculants (see example 1).

The tests, as well as confirming the self-preservative efficacy of thecomposition, also demonstrated that it increases with the reduction ofpH. Consequently, it is preferred that the cosmetic or detergentcomposition according to the invention has a pH less than or equal to 5,more preferably a pH in the range from 3.5 to 5.0.

The use of the above-indicated salts in the formulation of detergent orcosmetic compositions thus makes it possible to eliminate or in anyevent substantially reduce the concentration of the usualself-preservative agents the concentration of which, if present, willnevertheless be less than the threshold of irritant and/or sensitisingactivity.

Among the self-preservative agents commonly utilised in detergent orcosmetic compositions of the prior art, but absent from the compositionaccording to the invention, or at most present in non-irritant ornon-self-preservative concentrations are, for example, formaldehyde,chlorine, hypochlorite, compounds which release chlorine, chlorinedioxide, iodine and iodofers, phenol, cresol, chlorocresol, amphotericcompounds with self-preservative characteristics, chlorhexidine,peracetic acid and dihydroacetic acid, mercury compounds, alcohols,sorbic acid, benzoic acid, salicylic acid, boric acid, formic acid,crotonic acid and salts derived from the use, bronopol,5-bromo-5-nitrodioxane, hexamethylene tetramine, DMDM idantoine, variousinantoines such as MDM idantoine, chloracetamide, ureas such asimidazolidinyl urea and diazolidinyl urea, inorganic sulphites,triclosane, parabenes, isothiazolinones, usnic acid and its salts,chlorophene, hexachlorophene, dichlorophene, bromocheorophene,trichlorocarbon, chloroflourocarbon, benzamidines classified asself-preservatives, amines classified as self-preservatives,dimethyloxazolidine, ethylbicyeloxazolidine,dimethylhydroxymethylpyrazole, polyaminopropylbiguamide, sodiumhydroxy-methylglycinate, methyldibromoglutaronitrile, glycerylmonolaurate and their mixtures.

The non-irritant or non-self-preservative concentration varies independence on the compound considered, and can be easily determined bythe man skilled in the art since the above-listed compounds are allknown and usually utilised in cosmetics as self-preservatives.

In general it can be understood that a detergent or cosmetic compositionhas the desired hydrating characteristics when it is capable ofobviating the symptoms and manifestations of dry skin and hair(according to the definition of “hydrating compounds” in “A ShortTextbook of Cosmetology”, K. F. De Polo, first edition 1998).

The salts utilised in the present invention have such hydratingproperties.

The molecules of capryloyl glutamate and capryloyl hydrolysate, oncethey come into contact with the skin, in fact separate into glutamatesand hydrolysate on the one hand and fatty acid on the other.

Both wheat and rice hydrolysate protein and glutamic acid have hydratingproperties.

In fact, the protein hydrolysate, in contact with the skin, forms acontinuous protective layer over the corneal layer thereof, protectingit from external aggressions and increasing the hydration by reductionof TEWL (Trans Epidermal Water Loss). Moreover such protein hydrolysatesare sources of amino acid, which constitutes 40% of the naturalmoisturising factor (NMF). The glutamic acid on the other hand entersinto a series of biological cycles contributing to the correct hydrationof the skin and to maintenance of the natural cutaneous acidity thanksto the two to carboxylic groups. In fact, it constitutes 15% of thekeratins and forms part of the ε (γ-glutamyl) lysine bond present in thein involucrin and keratolin proteins which constitute the cellularmembrane of the corneal layer. It can be transformed into PCA, one ofthe components of the NMF, that is to say a set of water solublesubstances responsible for the correct hydration, as well as intoproline and hydroxyproline (these two amino acids are fundamental forthe synthesis of collagen and elastine). The acylglutamates, moreover,act as selective solvents for the principal component of the sebum,i.e., squalene, therefore leaving unaltered the functional lipids of thecorneal layer which control the hydration.

The caprylic acid component on the other hand performs its particularaction of controlling the increase of pathogenic micro-organisms,dandruff, body odours, the production of sebum and cutaneous disorders.

The use of salts of capryloyl glutamate and/or capryloyl hydrolysate ofwheat and/or rice protein in the formulation of the detergent orcosmetic compositions according to the invention thus make it possibleto eliminate or in any event substantially reduce the addition ofhydrating factors, emollients or palliatives for the skin,concentrations of which, if present, will nevertheless be less than theefficacious threshold for hydrating activity.

Among the hydrating agents commonly utilised in detergent or cosmeticcompositions of the prior art, but absent from the compositionsaccording to the invention, or at most present in non-efficaciousconcentrations, are, for example, glycerine, sorbitol, propyleneglycol,polyethylene glycol with molecular weight from 200 to 600, Sorbeth-30,urea, lactic acid and its salts, mucopolysaccharides such as ialuronicacid and chondroitin sulphate, orotic acid, lanolin, petrolatum, mineraloils, occlusive substances which hydrate the skin by preventing theevaporation of water, and their mixtures.

The concentration which is not efficacious for hydration varies independence on the compound considered, and can be easily determined bythe man skilled in the art since the above-listed compounds are allknown and commonly utilised in cosmetics as hydratants.

The detergent or cosmetic compositions according to the inventionpreferably include an aqueous medium, although the salts utilised canequally well be used in emulsions.

The total concentration of salts of capryloyl glutamate and/or capryloylhydrolysate of wheat and/or rice protein in the compositions accordingto the invention is preferably one which is sufficient in itself toconfer the desired self-preservative characteristics and hydratingaction, that is such as to confer the said characteristics incombination with other self-preservative and/or hydrating agents presentin concentrations which are not sufficient per se to confer suchcharacteristics.

This concentration lies preferably between 0.5% and 25% by weight ofactive substance with respect to the total composition, more preferablybetween 1.5% and 15% by weight of active substance. In this range ofconcentration, in fact, the salts present are able correctly to performall their functions.

The detergent or cosmetic compositions according to the invention caninclude at least one further and separate surfactant agent chosen fromanionic surfactants such as, for example, salts of alkyl sulphates andalkyl ether sulphates (for example sodium, magnesium, TEA, MEA andammonia salts), salts of amide/amide ether sulphates, salts of alkylsemisulphosuccinates and alkyl sulphosuccinates, salts of alkyl ethersemisulphosuccinates and alkyl ether sulphosuccinates, salts of acylamide semisulphosuccinates and of acyl amide sulphosuccinates, salts ofdodecyl benzene sulphonic acid, salts of alkyl/alkyl ethersulphoacetates, salts of sulphonated and/or sulphated organic molecules(for example, a-olefin sulphonates), salts of alkyl/alkyl ethercarboxylates, alkyl phosphonates, esters of phosphoric acid, salts ofacyl septionates; amphoteric surfactants, such as, for example, alkylbetaine, alkyl amidopropylbetaine, oxides of amine and of amides,amphocarboxyacetates and amphocarboxydiacetates, amphocarboxypropionatesand amphocarboxydipropionates; non-ionic surfactants such as, forexample, various amides, ethoxylated and non-ethoxylated fatty amines,ethoxylated nonylphenol, APG (alkyl polyglucosides), AEG (alkylethoxyglucosides), esters/ethers of fatty acids with glycerol and/orethoxylated and non-ethoxylated sugars, various ethoxylated/propoxylatedand non-ethoxylated/propoxylated esters, ethoxylated/propoxylated andnon-ethoxylated/propoxylated fatty alcohols, silicone molecules;cationic surfactants containing, for example, at least one atom ofquaternary nitrogen.

Some products in which the compositions of the inventions can be usedare: shampoo, foam baths, foam showers, washing up liquid, liquid soaps,solid soaps, lotions, emulsions of various types, balsams, productshaving simultaneous detergent and conditioning effects on the skinand/or hair, oils, emollient and detergent milks, face cream and/or bodycream and/or hair cream, detergents for intimate hygiene, brilliantine,permanent wave solutions, hair colouring, dentifrice, medicatedcosmetics and pharmaceutical products.

The examples which follow are provided solely for the purpose ofillustration and or not intended to limit in any way the scope of theinvention.

EXAMPLES Example 1 Test on the Self-Preservative Efficacy

To evaluate the self-preservative efficacy of sodium salts of capryloylglutamate a challenge test was conducted on a cosmetic compositioncomprising:

-   -   Sodium lauryl ether sulphate 20E (27% a.m.)=37%    -   Cocoamidopropyl betaine (30% a.m.)=5%    -   Sodium capryloyl glutamate (about 1.5% a.m.)=5%    -   Water=to 100%    -   pH=5.

Four mixed inoculations illustrated in the following table 1(gram+bacteria; gram−bacteria; yeasts; filamentary fungi) were preparedand each of these was inoculated with a specimen of the above-indicatedcomposition. TABLE 1 GRAM+ 1 × 10⁷ Staphylococcus aureas ATCC6538BACTERIA: Staphylococcusepidermidis ATCC 12228 GRAM− 1 × 10⁷ Escherichacoli ATCC 8739 BACTERIA: Pseudomonas aeruginosa ATCC 9027 Enterobactercloacae ATCC 13047 Pseudomonas putida (from cosmetics) YEASTS: 1 × 10⁷Candida albicans ATCC 10231 Saccharomyces cerevisiae ATCC 9763FILAMENTARY 1 × 10⁵ Aspergillus niger ATCC 16404 FUNGI: Penicilliumfuniculosum ATCC 9644The challenge test consists in monitoring the survival of the inoculantsover time; this survival is indicative of the self-preservative capacityof the cosmetic product during the period of use by the consumer.

In particular, survival of the inoculants was checked after 24 hours,seven days and 28 days from the inoculation. Monitoring at 24 hoursrepresents a datum for the purpose of evaluating the rapidity of theself-preservative system, that at 7 days indicates on the other hand thedegree of risk of pollution of the product, whilst the test at 28 days,as well as representing confirmation of the previously obtained data,makes it possible to show up the possible formation of resistantstrains.

The results obtained are illustrated in the following Table 2. TABLE 2Values obtained in the survival tests of the inoculations expressed incolony forming units per gram of product (c.f.u./g) Filamentary Gram+Gram− Fungi Yeasts Survival (c.f.u./g) (c.f.u./g) (c.f.u./g) (c.f.u./g)24 hours <10   10² <10   10²  7 days <10 <10 <10 <10 28 days <10 <10 <10<10

By successive dilutions the minimum inhibiting concentration (MIC) of anaqueous solution at pH 5 of sodium capryloyl glutamate against somemicro-organisms involved in the etiology of dandruff and some skin andrelated diseases was calculated. The results obtained are shown in thefollowing Table 3. TABLE 3 MICRO-ORGANISM MIC (%) Pytyrosporum ovale^(a) 4.5% Staphylococcus aureas ^(b) 1.5% Staphylococcus epidermidis^(b) 6.0% Propionibactrium acnes ^(b) 5.5% Pseudomonas aeruginosa ^(c)1.5%^(a)agent involved in the etiology of dandruff and in many skindisorders^(b)agent involved in the etiology of acne^(c)agent which determines pathological events above all in individualswith compromised immune defences; it is one of the principalprotagonists of hospital infections.

Example 2 Hydrating Face Cleaner Without Self-Preservatives

Sodium capryloyl glutamate (30% active material): 6%

Sodium cocoamphodiacetate (26% active material): 10%

Sodium lauryl sulphoacetate (65% active material): 1.5%

PEG-7 glyceril cocoate: 2%

Citric acid: as required to pH 5.0

NaCl: as needed

Colour and perfume: as needed

Water: to 100%

Example 3 Sebum Regulating Face Gel

Sodium capryloyl hydrolysate of rice protein (30% active material): 9%

Laurylmidopropyl betaine (30% active material): 20%

Sodium cocoamphodiacetate (26% active material): 3%

Cocoamidopropylaminooxide (30% active material): 10%

Citric acid: as needed to pH 5.0

NaCl, colour, perfume and water: to 100%

Example 4 Sports Shower Gel With Deodorant Effect

Potassium capryloyl hydrolysate of wheat protein (30% active material):6%

Laurylethoxysulphate of magnesium ethoxylate 2 moles (25% activematerial): 15%

Laurylamidopropyl betaine (30% active material): 20% PEG-7 glycerylcoccoate: 1%

Citric acid: as required to pH 4.5

NaCl, colour, perfume and water: to 100%

Example 5 Intimate Detergent

Salts of triethanolamine capryloyl hydrolysate of wheat protein (30%active material): 7%

Sodium capryloyl glutamate (30% active material): 3%

Laurylethoxysulphate of magnesium ethoxylate 2 moles (25% activematerial): 10%

Cocoamidopropyl betaine (30% active material): 6%

Disodiumlaurylethoxysemisulphosuccinate (30% active material): 4%

Citric acid: as need to pH 3.5 to 4.0

NaCl, colour, perfume and water: to 100%

Example 6 Anti-Dandruff Shampoo

Sodium capryloyl glutamate (30% active material): 10%

Laurylethoxysulphate of sodium ethoxylate 3 moles (27% active material):35%

Laurylamidopropyl betaine (30% active material): 5%

Laurylsulphate of ammonia (26% active material): 9%

DEA coccoamide (100% active material): 1%

Citric acid: as needed to pH 4.5

NaCl, colour, perfume and water: to 100%

Example 7

Potassium capryloyl hydrolysate of rice protein (30% active material):5%

Laurylethoxysulphate of sodium ethoxylate 3 moles (27% active material):30%

Potassium capryloyl glutamate (30% active material): 3%

Laurylsulphate of tri-ethanol amine (39% active material): 6%

Citric acid: as needed to pH 4.2

NaCl, colour, perfume and water: to 100%

Example 8 Antidandruff Shampoo

Potassium capryloyl glutamate (30% active material): 8%

Lauryamidopropyl betaine (30% active material): 10%

Laurylethoxysulphate of sodium ethoxylate 3 moles (27% active material):10%

Sodium lauryl sulphoacetate (65% active material): 1%

Lauryl sulphate of ammonia (26% active material): 10%

Citric acid: as needed to pH 5.0

NaCl, colour, perfume and water: to 100%

Example 8 Hand Wash

Sodium capryloyl hydrolysate of wheat protein (30% active material): 8%

Ethoxylated sodium lauryl ethoxysulphate 2 mole (27% active material):20%

Coccoamidopropylbetaine (30% active material): 4%

Citric acid: as needed to pH 4.0

NaCl, colour, perfume and water: to 100%

1. Use of capryloyl glutamate and/or capryloyl hydrolysate salts ofwheat and/or rice proteins as self-preservative and hydrating agents andsimultaneously as sebum regulating, anti-dandruff and/or anti-odouragents in a detergent or cosmetic composition which is free from otherself-preservative agents and other hydrating agents, or which comprisesother self-preservative and/or hydrating agents in a non-efficaciousand/or insufficient concentration to confer the desiredself-preservative and/or hydration characteristics in an analogous orsimilar composition free from the said salts.
 2. Use according to claim1, wherein the said salt is selected from the group consisting of: saltswith alkaline metal cations or other monovalent cations such as Cu⁺;salts with alkaline earth metal cations or other bivalent cations suchas Pb²⁺; salts with trivalent cations such as Al³⁺; salts withpolyvalent cations such as Sn⁴⁺; salts with NH⁴⁺ or with an amino baseselected from tri-ethanol amine, monethanol amine, diethanol amine,monoisopropanol amine, tri-isopropanol amine, 2-amino butanol, aminoethyl propanediol, arginine, lisine, ornithine, amino methyl propanol,amino methyl propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol; andtheir combinations.
 3. Use according to claim 1, wherein the saiddetergent or cosmetic composition further includes an aqueous medium. 4.Use according to claim 1, wherein the said detergent or cosmeticcomposition has a pH value less than or equal to
 5. 5. Use according toclaims 1, wherein the said further hydrating agent is selected from thegroup consisting of: glycerine, sorbitol, propylene glycol, polyethyleneglycol with molecular weight from 200 to 600, Sorbeth-30, urea, lacticacid and its salts, mucopolysaccharides such as ialuronic acid andchondroitin sulphate, orotic acid, lanolin, petrolatum, mineral oils,occlusive substances which hydrate the skin by preventing theevaporation of water, and their mixtures.
 6. Use according to claim 1,wherein the said further self-preservative agent is selected from thegroup consisting of: formaldehyde, chloride, hypochlorite, compoundsreleasing chlorine, bioxide of chlorine, iodine and iodophers, phenol,cresol, chlorocresol, amphoteric compounds with self-preservativecharacteristics, chlorhexidine, peracetic acid and dihydroacetic acid,compounds of mercury, alcohols, sorbic acid, benzoic acid, salicylicacid, boric acid, formic acid, propionic acid and salts derived fromthese, bronopol, 5-bromo-5-nitrodioxane, hexamethylene tetramine, DMDMidantoine, various idantoines such as MDM idantoine, chloracetamide,ureas such as imidazolidinyl urea and diazodinyl urea, inorganicsulphites, trichlosane, parabenes, isothiazolinones, usnic acid and itssalts, chlorophene, hexachlorophene, dichlorophene, bromochlorophene,trichlorocarbon, chlorofluorocarbon, benzamidines classified asself-preservatives, amines classified as self-preservatives,dimethyloxazolidine, ethylbicycloxazolidine, dimethyl hydroxymethylpirazol, polyaminopropyl biguanide, sodium hydroxymethylglycinate,methyldibromoglutaronitrile, glyceryl monolaurate and their mixtures. 7.Use according to claim 1, wherein the said detergent or cosmeticcomposition includes a further and separate surfactant agent selectedfrom anionic, cationic, non-ionic, amphoteric surfactants and theirmixtures.
 8. Use according to claim 7, wherein the said further andseparate surfactant agent is selected from sodium laurylsulphate, sodiumlaurylethoxysulphate and their mixtures.
 9. Use according to claim 1,wherein the concentration of the said salt in the said detergent orcosmetic composition is in the range from 0.5 to 25% by weight of activematerial with respect to the total weight of the composition.
 10. Useaccording to claim 9, wherein the said concentration is in the range of1.5 to 15% by weight of active material.